Light-sensitive color photographic material



Patented Sept. 7, 1954 LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIAL KarlOtto Gauguin and Eric Macdonald, Blackley, Manchester, England,assignors to Imperial Chemical Industries Limited,. a corporation ofGreat Britain No Drawing. Application November13, 1951, Serial No.256,127

Claims priority, application Great Britain November 20, 1950 Claims.

This invention relates to colour photography and more particularly to asimplified multilayer material for use in colour photography.

In multilayer photographic films or paper adapted for use. in colourphotography which comprise differently sensitised emulsion layersmounted on a film base or paper and wherein the uppermost layer is usedfor forming the blue record, a yellow filter layer is usually employedbetween the uppermost (blue sensitive) layer and the other sensitivelayers, which in addition to being sensitised to other parts of thespectrum are also sensitive to blue light. The yellow filter layerabsorbs the blue light and prevents it striking these lower sensitivelayers.

The coating of the yellow filter layer itself provides an undesirablecomplication of the process of manufacture of .the photographic film orpaper and when colloidal silver is used in theyellow filter layer, as isusual in commercial processes, further complications are-- introduced bythe necessity of coating separationlayers between. the filter layer andthe light sensitivelayers to avoid fogging. of the sensitive emulsionsby the colloidal silver.

It is known that when a yellow dyestuff, even invhighconcentration, isintroduced into a single light-sensitive gelatino-silver halide emulsionlayer, the layer is still partiallysensitive tov the blue light strikingthe light sensitive silver halide at or near the surface ofthelayer, butwe have found that whena blue sensitive layer is coated on top of alightsensitive layer containing a yellow styryl dyestufi as hereinafterdefined the latter layer is entirely or almost unaffected by normalexposureto blue light which .-has.passed through the superimposed. bluesensitive layer. By a blue sensitivelayer we mean a layer of lightsensitive. gelatino-silver halide emulsion which has not been speotrallysensitised to parts of the spectrum other than blue.

According to our inventionwe provide a photographic material adapted foruse in colour photography which comprisesthree differently sensitisedvgelatinoesilver halide .emulsion layers containin yellow, magenta andcyan colour formers superimposed on a support, characterised in that oneof the outermost sensitive layers is sensitive to blue light and isadjacent to, and; not separated by a filter layer from the middlesensitive layer which middle sensitive layer contains a yellow styryldyestuif as hereinafter defined.

The yellow styryl dyestuffs used in; the process of the presentinvention which function both as a yellow filter 'dyestuff and asamagenta colour former arethe water'soluble dyestuffs which carry asubstituent rendering the dyestuff' non-diffusible, for example asubstituent containing an alkyl chain of at least 5 carbon atoms, andwhich are obtainable by condensing a reactive methylene compound with ananil of a Water-soluble or alkali-soluble aldehyde of the formula andwherein at least one of the radicals R1 and.

R2 is an alkyl radical substituted with for exam-. ple, CN, COOAlkyl,NO2 carboxyl or sulphonic acid groups, and, when only one. of theradicals R1 and R2 is an alkyl radical so substituted, the other radicalisa substituted or unsubstituted hydrocarbon radical.

Suitable styryl'dyestufis may be obtained by condensing an anil of ap-substituted-aminobenzaldehyde with a reactive methylene compound ofthe kind used for forming magenta dyestuffs in colour photography byreaction with colour developers. These reactive methylene compounds maybe for example, compounds of the pyrazolone series or of thecyanoacetylseries.

Specific examples of suitable reactive methylene compounds are1(4=-phenoxy-3-sulphophenyl) -3-heptadecyl 5-pyrazolone, l-(phenyl-3'-methanesulphonic acid) -3 heptadecyl-5-pyrazolone, and the compoundobtained by acylating d-omega-cyanoacetaniline with octadecenylsuccinicanhydride.

As suitable p-substituted-amino-benzaldehydes there may be mentioned forexample p-(N- methyl N sulphoethyl amino) -benzaldehyde, p-(N :N 5:5disulphodiethylamino) -benzaldehyde, 4-(NzN' 6:18disulphodiethylamino)-2- methyl benzaldehyde,p-(N-methyl-N-carboxyethylamino)-benzaldehyde, p-(N:N-;9:;8.'dicarboxydiethylamino) -benzaldehyde, p-N :N-di(carboxymethyD-aminobenzaldehyde, p-(N-B-sulphoethylamino) benzaldehyde, 4 (N:N 6:5-dichlorodiethylamino) -2-sulpho-benzaldehyde.

p-NzN-di-(carboxymethyl) -amino benzaldehyde may be made by introducingthe aldehyde group into di-(ethylcarboxymethyl) -aniline by the methodof Vilsmeier and Haaok (Berichte, volume 60, page 119) and hydrolysingthe diester so obtained. Ihe other monoor di-(carboxyalkyl) derivativesmay be made by hydrolysis of the appropriate cyanoalkyl compounds whichmay be made by treating the corresponding hydroxyalkyl ordihydroxydialkyl anilines with phosphorus pentabromide, treating thecorresponding bromoalkyl or dibromodialkyl compounds so obtained withpotassium cyanide, and introducing the aldehyde group by reaction withphosphorus oxychloride and N-methylformanilide and subsequenthydrolysis, that is to say by the methods of Vilsmeier and Haack(Berichte, volume 60, page 119). The monoand di-(sulphoalkyl)derivatives may be made by the action of sodium sulphite on thecorresponding chloroalkyl compounds.

It will be apparent that if the top layer is blue sensitive, thematerial will be exposed in the normal way to light, but if the bottomlayer is blue sensitive, the material will be exposed to light throughthe support.

In one embodiment of our invention in which the photographic material isespecially valuable for use in the production of colour positivetransparencies and prints, there are 3 sensitive layers superimposed onthe support, the top layer being blue sensitive (that is not spectrallysensitised) and containing a yellow colour former, the middle layercontaining a styryl dyestuff as hereinbefore defined, which serves bothas a yellow filter dyestufi and as a magenta colour former and thebottom layer containing a cyan colour former, either the middle layer orthe bottom layer being red sensitive and the other being greensensitive.

Such a photographic material may be exposed and processed by known meanswhen the filter dyestuff is largely discharged in the developingprocess. To ensure complete discharge of the dyestuff the material, may,if desired, be treated after the development step with hydrazine hydratewhich may if desired be added to the fixing bath.

If the spectral absorption of the magenta dyestuiT obtained from theyellow styryl dyestuff is not entirely suitable for a positive print ortransparency, then some modification is possible by the addition to theyellow styryl dyestuff of a small proportion of a colourless colourformer yielding a suitable magenta dyestuil.

In a second embodiment of our invention, in which the photographicmaterial is especially valuable for the production of negativetransparencies, there are 3 sensitive layers superimposed on a support,the top layer being blue sensitive (that is not spectrally sensitised)and containing a yellow colour former, the middle layer containing amixture of a yellow styryl dyestufi as hereinbefore defined and a yellowstyryl dyestuff derived from a reactive methylene compound and awater-insoluble and alkali-insoluble p-N-substituted amino-benzaldehyde,and the bottom layer containing a cyan colour former, either the middlelayer or the bottom layer being red sensitive and the other being greensensitive.

Examples of suitable water-insoluble and alkali-insolublep-N-substituted amino-benzaldehyde are p-(N-methyl-N-fi-hydroxyethylamino) benzaldehyde, p-(N-ethylN Bhydroxyethylamino) -benzaldehyde, p- (,3 c-dihydroxydiethylamino)-benzaldehyde, p- (N-methyl-N-methoxyethylamino) -benzaldehyde, p-(N-ethyl-N-methoxyethylamino) -benzaldehyde, p- (N-butyl-N-fihydroxyethylamino) -benzaldehyde, p- (N-methyl-N-e-chloroethylamino)-benzaldehyde, p-(N- ethyl-N-c-chloroethylamino) -benzaldehyde, p- (13:3 dichlorodiethylamino) benzaldehyde, 4- (fi:;3' dichlorodiethylamino) 2methylbenzaldehyde, p- (N methyl-N-fl-cyanoethylamino) benzaldehyde, p(5: 3 dicyanodiethylamino) benzaldehyde and p di (ethylcarboxymethyl)amino-benzaldehyde.

Such a photographic material may be exposed and developed, bleached andfixed by known means and then treated with formaldehyde or sodiumnitrite when a yellow colour correction mask is formed in the middlelayer. It is su gested as a possible explanation of this process thatboth styryl dyestuifs function as filter dyestuffs and colour formersand that in the development with an aromatic amine as developer, magentaimages are formed in the exposed parts of the middle layer by the actionof the oxidation product of the developer on the styryl dyestuffs andthe rest of the styryl dyestuffs are decomposed by the developer to givethe parent reactive methylene compounds and also anils formed from theparent aldehydes by reaction with the developer. The anil from thesoluble aldehyde is washed out from the photographic material during theprocessing steps. The insoluble aldehyde is liberated from thecorresponding anil by the action of formaldehyde or sodium nitrite andit then reacts with the reactive methylene compound to re-form theyellow styryl dyestuiT. Since the concentration of residual reactivemethylene compound Will be much higher in the counter-imagewise parts ofthe layer than in the imagewise parts (where it has been used forforming magenta dyestuffs) then the intensity of yellow styryl dyestuffformed will be higher in the counter-imagewise parts and accordinglythe, styryl dyestuiT will form a colour correction masking image.

It will be apparent that the strength of the masking image can becontrolled by adjusting the proportions of the two styryl dyestuffs inthe layer.

The invention is illustrated but not limited by the following examplesin which the parts are by weight:

Example 1 A multilayer light sensitive photographic paper is made up asfollows:

A red sensitive gelatino-silver halide emulsion layer containing 10grams per litre of the sodium salt of the cyan colour forming componentl-hydroxyl-sulpho- 2 naphthoyloctadecylamide is coated on a papersupport and on this layer there is coated a gelatin separation layer andsubsequently a green sensitive gelatino-silver halide emulsion layercontaining 15 grams per litre of the sodium salt of the yellow styryldyestuff 1- (4'-phenoxy-3'-sulphophenyl) -3-heptadecyl 4 p N:N- di(carboxyethyl) aminobenzylidene-S-pyrazolone, to act both as the magentacolour forming component and also as the yellow filter dyestuff. Agelatin separation layer is then coated and finally as the top layerthere is coated a blue sensitive gelatino-silver halide emulsioncontaining 10 grams per litre ofp-stearylamino-benzoylacetanilide-p'-carboxylic acid sodium salt, theyellow colour forming component described in Example 3 of Britishspecification No. 486,848.

The paper is exposed to the light transmitted by a subtractivelycoloured negative transparency and then developed in a solution of thefollowing composition:

The paper 'is rinse'd and transferred *toa stop bath or the followingcomposition:

Parts "Acetic acid, glacial -15 i'Sodium'acetate -'-30 I Water tomake'upto 1000 The paper is washed-and transferred toa bleach- .ing' solutionof the following composition:

The paper is further washed andltreatedulna fixing anddyestuff-discharee solutionof the following composition:

Parts Sodium thiosulphate H200 50% hydrazinelhydrate solution .100 Waterto make upto 1.000

The paper is finally washed and dried when a positive paper print isobtained.

Example? ,A .multilayer light sensitive photographic ,material'is madeup as'follows:

.A red sensitive gelatino-silverhalideemulsion .layercontaining gramsper litre of the sodium salt or the cyan colourformingcomponent-obtained by condensing 'l-hydroxy-z-naphthoic acid-chloridewith oleylamine and sulphonating (that is the colour formingcomponentdescribed in Example 10 of British specification No. 465,823)is coated on a transparent support and on this layer there is coated agreen sensitive gelatino-silver halide emulsion layer containing 12grams per litre of the styryl dyestufi 1-(4- phenoxy 3' sulphophenyl) 3heptadecyl- 4 p di( 8 cyanoethyl) amino benzylidene- 5-pyrazolone sodiumsalt, derived from the insoluble aldehyde p-di-(B-cyanoethyl)-amino-benzaldehyde and 5 grams per litre of the styryl dyestuff 1-(4-phenoxy-3 -sulphophenyl) -3-heptadecyl 4 p di (oarboxyethyl) aminobenzylidene-S-pyrazolone sodium salt, derived from the soluble aldehydep-(5:/3-dicarboxydiethylamino)-benzaldehyde. This layer serves as ayellow filter layer, and provides the magenta colour forming componentsand also the yellow masking dyestufi. Finally as the top layer there iscoated a blue sensitive gelatino-silver halide emulsion containing 10grams per litre of p-stearylamino-benzoy1acetanilide 3p carboxylic acidsodium salt (the yellow colour forming component described in Example 3of British specification No. 486,848) The film is exposed to the lightfrom a coloured object and developed in a developer solution of thefollowing composition:

Parts 3 1 p-N N diethylaminoaniline hydrochloride- Sodium sulphite,anhydrous Sodium carbonate, anhydrous 60 Potassium bromide 2 Water tomake up to 1000 6 ofthe developer solution has been-removedr duing theprocessing" and washing steps.

The processed material contains in the first layer a cyandyestuif.,negative image, in the second layer a magenta dyestufinegative image and a yellow styryl dyestufi positive image and in theetopzlayer:a;yellowz:dyestuff :negative' image.

Trample 3 Al-multilayer material madeeup. asidescribed win:; Examplei.1,',.but -in.p1ace of :the;. y.el1ow styryl .dyestuff: described there.is used-215 grams ;per.llitre of the :dyestuffs-l-;3voctadecenyl-sucoinamidoel-::omega-cyanoeomega-dpeN,:N-di-idarboxyethyl)eamino-benzylidenelnacetobenzenetsodium @salt). The l- 'paper-dsexposedto the {light transmittedrby aesubtractively. coloured,negativetransparency and :thendeveloped ina-solution otthe followingcomposition:

:Barts :5+diethylamino-z-aminotoluene hydrochloiillide 1; 2.5 -;Sodiumsulphitecanhydrous 2 :Hydroxylamine hydrochloride 1 -:Sodium carbonate,zanhydrous M .60 Potassium:bromide ..,-2 -Waten'to.makerup-ton10 .0

The paper is-"rinsed and transferred =to-a-stop bath of thefollowing'composition:

Parts Potassium ferricyanide 1 00 "Potassium'bromi'cle Sodium dihydrogenphosphate '50 -"*Watertomake;up"to -1'000 Parts Sodium thiosulphate 200hydrazine hydrate solution Water to make up to 1000 The paper is finallywashed and dried, when a positive paper print is obtained.

Example 4 In addition to the yellow styryl dyestuff of Example 3 theremay be added 3 grams of the colourless colour former1-(4-phenoxy-3'-sulphophenyl) 3 heptadecyl-S-pyrazolone(sodium salt).

What we claim is:

l. A photographic material adapted for use in colour photography whichcomprises three superimposed differently sensitized gelatino-silverhalide emulsion layers, the layers comprising a middle sensitive layerbetween two outermost sensitive layers, said layers containing colourformers which couple with the oxidation product of a primary aromaticamino developer to form the color image and are adapted to yield, uponexposure and development, yellow, cyan and magenta coloured images inseparate layers, said material being characterized in that one of theoutermost sensitive layers is sensitive to blue light and is adjacentto, and not separated by a filter layer from, the middle sensitivelayer, which middle sensitive layer contains a water-soluble yellowstyryl dyestuff carrying a substituent which renders the dyestufinon-difiusible and obtainable by condensing a reactive methylenecompound selected from the group consisting of compounds of thepyrazolone and cyanoaeetyl series, with an anil of an aldehyde selectedfrom the group consisting of water-soluble and alkalisoluble aldehydesof the formula:

wherein R is selected from the group consisting of an unsubstitutedmonocyclic aryl radical and a sulphonic acid substituted monocyclic arylradical, at least one of the radicals R1 and R2 is a substituted alkyl,said substituent being selected from the group consisting of cyano,carboxy alkyl, nitro, chloro, carboxyl and sulphonic acid groups, andwhen only one of the radicals R1 and R2 is said substituted alkyl, theother radical is a hydrocarbon radical wherein one of R, R1 and R2 inall cases contains a member from the group consisting of carboxyl andsulphonic acid groups in the case of R1 and R2 and-a sulphonic acidgroup in the case of R.

2. A photographic material as defined in claim 1, wherein the top layeris blue sensitive and contains a colour former adapted to yield a yellowcoloured image upon exposure and development and the bottom layercontains a colour former adapted to yield a cyan coloured image uponexposure and development, one of the layers other than the top layerbeing red sensitive and the other layer being green sensitive.

3. A photographic material as described in claim 2, wherein the middlelayer contains a colourless colour former in addition to the styryldyestufif.

4. A photographic material as described in claim 1, wherein the toplayer is blue sensitive and contains a colour former adapted to yield ayellow coloured image upon exposure and development, the bottom layercontains a colour former adapted to yield a cyan coloured image uponexposure and development, and the middle layer contains a mixture ofsaid yellow styryl dyestufi and a yellow styryl dyestufi which is thecondensation product of a reactive methylene compound and awater-insoluble and alkaliinsoluble p-N-substituted amino-benzaldehyde,the substituent on the p-N atom being selected from the group consistingof alkyl, chloroalkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl, and alkylcarboxyalkyl groups, one of the layers other than the top layer beingred sensitive and the other layer being green sensitive.

5. The photographic material as described in claim 4, wherein thecondensation product of the reactive methylene compound and thewaterinsoluble and alkali-insoluble p-N-substituted amino-benzaldehydecontains a substituent which renders the dyestuff non-difiusible.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,036,546 Schneider Apr. '7, 1936 2,186,731 Schneider Jan. 9,1940 2,428,054 Vittum et a1 Sept. 30, 1947 2,449,966 Hanson Sept. 21,1948 FOREIGN PATENTS Number Country Date 513,596 Great Britain Oct. 17,1939

1. A PHOTOGRAPHIC MATERIAL ADAPTED FOR USE IN COLOUR PHOTOGRAPHY WHICHCOMPRISES THREE SUPERIMPOSED DIFFERENTLY SENSITIZED GELATINO-SILVERHALIDE EMULSION LAYERS, THE LAYERS COMPRISING A MIDDLE SENSITIVE LAYERBETWEEN TWO OUTERMOST SENSITIVE LAYERS; SAID LAYERS CONTAINING COLOURFORMERS WHICH COUPLE WITH THE OXIDATION PRODUCT OF A PRIMARY AROMATICAMINO DEVELOPER TO FORM THE COLOR IMAGE AND ARE ADAPTED TO YIELD, UPONEXPOSURE AND DEVELOPMENT, YELLOW, CYAN AND MAGENTA COLOURED IMAGES INSEPARATE LAYERS, SAID MATERIAL BEING CHARACTERIZED IN THAT ONE OF THEOUTERMOST SENSITIVE LAYERS IS SENSITIVE TO BLUE LIGHT AND IS ADJACENTTO, AND NOT SEPARATED BY A FILTER LAYER FROM, THE MIDDLE SENSITIVELAYER, WHICH MIDDLE SENSITIVE LAYERS CONTAINS A WATER-SOLUBLE YELLOWSTYRYL DYESTUFF CARRYING A SUBSTITUENT WHICH RENDERS THE DYESTUFFNON-DIFFUSIBLE AND OBTAINABLE BY CONDENSING A REACTIVE METHYLENECOMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THEPYRAZOLONE AND CYANOACETYL SERIES, WITH AN ANIL OF AN ALDEHYDE SELECTEDFROM THE GROUP CONSISTING OF WATER-SOLUBLE AND ALKALISOLUBLE ALDEHYDESOF THE FORMULA: